US6716935B1 - Continuous process for the production of controlled architecture materials under high solids loading conditions - Google Patents

Continuous process for the production of controlled architecture materials under high solids loading conditions Download PDF

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US6716935B1
US6716935B1 US10/324,242 US32424202A US6716935B1 US 6716935 B1 US6716935 B1 US 6716935B1 US 32424202 A US32424202 A US 32424202A US 6716935 B1 US6716935 B1 US 6716935B1
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monomer
reactor
temperature
reaction mixture
methacrylate
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James Michael Nelson
Ryan E. Marx
Michael John Annen
Duane Douglas Fansler
Maureen Ann Kavanagh
Babu Nana Gaddam
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to US10/324,242 priority Critical patent/US6716935B1/en
Priority to AU2003291543A priority patent/AU2003291543A1/en
Priority to KR1020057011333A priority patent/KR20050085763A/ko
Priority to MXPA05006329A priority patent/MXPA05006329A/es
Priority to BRPI0317115-9A priority patent/BR0317115B1/pt
Priority to JP2004564999A priority patent/JP2006511657A/ja
Priority to EP03768949.4A priority patent/EP1572750B1/en
Priority to PCT/US2003/036479 priority patent/WO2004060927A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00081—Tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel

Definitions

  • the present invention relates to a continuous process for the production of polymer using high solids loadings of polymerizable monomers in a stirred, plug-flow, temperature-controlled reactor.
  • polymers can be prepared from different monomeric materials, the particular type formed being generally dependent upon the procedures followed in contacting the materials during polymerization.
  • random copolymers can be prepared by the simultaneous reaction of the copolymerizable monomers.
  • Block copolymers are formed by sequentially polymerizing different monomers.
  • Useful classes of polymers can be synthesized via anionic, cationic, and free-radical methods.
  • Controlled architecture refers to a polymer with a designed topology (linear, branched, star, combination network), composition (block copolymer, random copolymer, homopolymer, graft copolymer, tapered or gradient copolymer), and/or functionality (end, site specific, telechelic, multifunctional, macromonomers).
  • topology linear, branched, star, combination network
  • composition block copolymer, random copolymer, homopolymer, graft copolymer, tapered or gradient copolymer
  • functionality end, site specific, telechelic, multifunctional, macromonomers
  • axial mixing means mixing in a direction parallel to the overall direction of flow in a reactor
  • block copolymer means a polymer having at least two compositionally discrete segments, e.g., a di-block copolymer, a tri-block copolymer, a random block copolymer, and a star-branched block copolymer;
  • branching agent means a multifunctional anionically polymerizable monomer or multifunctional quenching or coupling agent, the addition of which results in the formation of starbranched polymer
  • “continuous” means that reactants enter a reactor at the same time (and, generally, at the same rate) that polymer product is exiting the same reactor;
  • di-block copolymer or “tri-block copolymer” means a polymer in which all the neighboring monomer units (except at the transition point) are of the same identity, e.g., -AB is a di-block copolymer comprised of an A block and a B block that are compositionally different, ABA is a tri-block copolymer in which the A blocks are compositionally the same, but different from the B block, and ABC is a tri-block copolymer comprised of A, B, and C blocks, each compositionally different;
  • “high solids loading” refers to a solution in which the initial reactants and/or reaction products comprise more than 50 wt % solids to an upper limit of 100 wt % solids;
  • living anionic polymerization means, in general, a chain polymerization that proceeds via an anionic mechanism without chain termination or chain transfer. (For a more complete discussion of this topic, see Anionic Polymerization Principles and Applications . H. L. Hsieh, R. P. Quirk, Marcel Dekker, NY, N.Y. 1996. Pg 72-127);
  • living end means a polymerizable reactive site , present in the absence of termination at the end of a polymer chain
  • oligomeric means a polymer molecule consisting of only a few monomer units (e.g., dimers, trimers, tetramers);
  • plunge means a three dimensional slice of the reaction mixture
  • PFR plug flow reactor
  • polydispersity means the weight average molecular weight divided by the number average molecular weight; polydispersity is reported on a polydispersity index (PDI);
  • radial mixing means mixing in a direction perpendicular to the overall direction of flow in a reactor
  • random block copolymer means a copolymer having at least two distinct blocks wherein at least one block comprises a random arrangement of at least two types of monomer units;
  • reaction zone means that portion of a reactor or reactor system where the majority of reaction occurs
  • reaction time means the time necessary for a theoretical plug of reaction mixture to pass completely through a reactor
  • segment refers to a block of polymer formed by the addition of a specific monomer or a branching agent
  • starbranched polymer means a polymer consisting of several linear chains linked together at one end of each chain by a single branch or junction point (See Anionic Polymerization Principles and Applications . H. L. Hsieh, R. P. Quirk, Marcel Dekker, NY, N.Y. 1996. Pg 333-368);
  • star-branched block polymer or “hyper-branched block copolymer” means a polymer consisting of several linear block chains linked together at one end of each chain by a single branch or junction point, also known as a radial block copolymer (See Anionic Polymerization Principles and Applications . H. L. Hsieh, R. P. Quirk, Marcel Dekker, New York, N.Y. 1996. Pg 333-368);
  • temperature-sensitive monomer means a monomer susceptible to significant side reactions of the living ends with reactive sites, such as carbonyl groups, on the same, or a different, polymer chain as the reaction temperature rises;
  • temperature profile means the temperature or temperatures experienced by a reaction mixture plug over time as it moves through a reactor.
  • An advantage of at least one embodiment of the present invention is that the ability to control architectures at high solids offers increased convenience and favorable environmental considerations.
  • An advantage of at least one embodiment of the present invention is that the temperature of the reaction mixture can be controlled to such an extent that side reactions are minimized. This is especially advantageous when temperature-sensitive monomers are used.
  • Another advantage of at least one embodiment of the present invention is that the average molecular weight of resulting polymers can be controlled well by controlling the amount of initiator added to the reaction mixture.
  • Another advantage of at least one embodiment of the present invention is that various polymer architectures can be tailored and synthesized to be suitable for specific applications.
  • Another advantage of at least one embodiment of the present invention is that the ability to control the temperature enables the reaction materials to be maintained in solution, which facilitates the desired reaction.
  • FIG. 1 is a schematic representation of an exemplary reaction system useful for carrying out the polymerization process of the present invention.
  • High solids loadings are typically estimated as (grams of monomer)/(grams of monomer+grams of solvent+grams of initiator) and are typically measured as (polymer)/(polymer+solution).
  • polymerizations under high solids loading conditions are performed in extruders.
  • working with high solids loading of flammable monomers can be difficult because extruders typically have limited heat transfer capabilities. If the reaction system retains heat, flammable monomers may ignite or degrade. Additionally, it is difficult to achieve plug flow in an extruder due to a high likelihood of materials being retained in the flights and mixing elements, which results in reactor fouling. Reactor fouling becomes a serious issue at high monomer concentrations, due to the lack of the presence of a heat sink, resulting in poor heat transfer, which results in hot spots and increased fouling.
  • the average molecular weight of the resultant polymeric material is established by controlling the monomer to initiator ratio. This ratio is established by controlling the respective monomer and initiator flow rates. Narrow molecular weight distributions can be obtained by controlling the temperature of the reaction mixture. Avoiding high temperatures minimizes unwanted side reactions that can result in polymer chains having differing molecular weight averages.
  • Polydispersity can be influenced by the reaction kinetics of the reaction mixture and the minimization of side reactions, especially when temperature sensitive monomers are present. Maintaining optimum temperatures in each zone of the reactor can positively influence reaction kinetics. Maintaining optimum temperatures can also advantageously affect the solution viscosity and the solubility of the reactants.
  • the structure of the polymerized organic material is determined by the sequence of monomer addition(s). Homopolymers are formed when only one monomer type is used, random copolymers when more that one monomer type is introduced simultaneously, and segmented block copolymers when more than one monomer type is introduced sequentially.
  • the temperature profile of the reactor be controllable over time and that the reaction mixture be impelled in a relatively plug flow manner through the reactor. This allows the reaction mixture in the reactor at a given location to be subjected to the same reaction conditions as those encountered by previous and subsequent reaction mixture portions as they pass by the same location.
  • Maintaining temperature control and movement of the reaction mixture in an essentially plug flow manner can be complicated by the exothermic nature of the type of reaction being performed.
  • Some polymerization methods involving polar monomers are complicated by side reactions and an ordering phenomenon associated with the aggregation of materials in solution as micelles. This ordering phenomena becomes even more prevalent at high solids than when block or end functional architectures are diluted by solvent. Micelle formation can be dissipated by the presence of suitable polar solvents.
  • Block and homopolymer systems often form gels under batch or semi-batch conditions at high solids due to side reactions such as chain-chain coupling, manifested as a result of poor mixing and poor heat dissipation or transfer.
  • side reactions such as chain-chain coupling
  • heat dissipation or transfer In general, in batch systems, which lack good mixing capabilities, the probability of forming block structures are lessened at higher solids, due to viscosity issues. Again, homopolymer contaminants result in these poorly mixed systems.
  • Starbranched polymers although once formed typically display lower solution and melt viscosity, are very sensitive to gelation events. For example, during convergant star polymer synthesis in which living anionic polymer chains are coupled by difunctional monomers, chain-chain coupling and gels can result if insufficient mixing and heat transfer are not provided
  • polymers containing polar side-chain and end-group functionality are also of particular importance for commercial applicability.
  • Polymers containing functional groups can have considerable commercial applicability, finding uses as dispersants, blend compatibilizers, surfactants, surface modifiers, colloidal stabilizers, stain release agents, encapsulants, binding agents, viscosity modifiers, and (in some cases) precursors to ionomers.
  • Important synthetic targets within this area are polymers containing carboxylic acid, hydroxyl, amine or thiol segments, due to their high polarity and water miscibility.
  • the present invention overcomes many of the problems associated with the foregoing polymerizations because it provides intensive mixing to aid in processing the materials and overcoming viscosity issues such as aggregation due to hydrogen bonding. Also it allows for the temperature control of a series of reaction zones so that one zone can be cooled to control an exotherm, then, if necessary, another zone can be heated, for example, to promote the solubility of hydrogen-bonded materials such as high molecular weight materials and co-monomers that are incorporated at high concentrations
  • Adequate mixing and temperature control promote the ability to reproduce the same materials, e.g., having a similar average molecular weight and having a narrower polydispersity index (PDI) than obtained without temperature control.
  • PDI polydispersity index
  • the PDI of the polymers of this invention is less than 3, more preferably less than 2, and most preferably less than 1.5.
  • One suitable plug-flow, temperature-controlled reactor is a stirred tubular reactor (STR). Any type of reactor, or combination of reactors, in which a reaction mixture can move through in an essentially plug flow manner with radial mixing is also suitable. Combinations of STRs, including combinations with extruders, also may be suitable.
  • the temperature or temperature profile of the reactor is preferably controllable to the extent that a plug of the reaction mixture in a particular location within the reaction zone (i.e., the portion of the reaction system where the bulk of polymerization occurs) at time t 1 will have essentially the same temperature or temperature profile as another plug of the reaction mixture at that same location at some other time t 2 .
  • the reaction zone can include more than one temperature-controlled zone of the reactor.
  • STRs may provide for essentially plug flow of the reaction mixture and can be configured such that good temperature control can be attained, and are therefore useful in getting the average molecular weight of the polymer product to remain close to a target value, i.e., have a narrow polydispersity range.
  • reaction system 10 includes reaction mixture delivery system 20 , optional heat exchanger 30 , reactor 40 , optional devolatilization mechanism 50 , outlet 60 , and optional recycle stream 70 , which allows residual solvent to be recycled through the system.
  • Reaction mixture delivery system 20 comprises component feed supply units 12 a - 12 g , purification units 14 a - 14 e , and pumps 16 a - 16 g .
  • the manner in which these elements are combined and controlled helps to provide, consistently over time, control over the average molecular weight distribution of the polymer produced by the described process.
  • the polydispersities of the resulting polymers can be minimized. Polydispersity indexes of less than 3, preferably less than 2, most preferably less than 1.5 may be achieved.
  • Suitable starting monomeric materials include those that can be used to make controlled architecture materials (CAM), which are polymers of varying topology (linear, branched, star, star-branched, combination network), composition (di-, tri-, and multi-block copolymer, random block copolymer, random copolymers, homopolymer, graft copolymer, tapered or gradient copolymer, star-branched homo-, random, and block copolymers), and/or functionality (end, site specific, telechelic, multifunctional, macromonomers).
  • CAM controlled architecture materials
  • the invention allows the synthesis of polymers by step growth polymerizations, specifically traditional or living/controlled free radical, group transfer, cationic or living anionic polymerizations.
  • step growth polymerizations specifically traditional or living/controlled free radical, group transfer, cationic or living anionic polymerizations.
  • the most industrially relevant methods are traditional or living/controlled free radical and living anionic polymerizations.
  • Specific free radical methods of making the polymers include atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), and nitroxyl- or nitroxide- (Stable Free Radical (SFR) or persistent radical-mediated polymerizations. These controlled processes all operate by use of a dynamic equilibrium between growing radical species and various dormant species (see Controlled/Living Radical Polymerization, Ed. K. Matyjaszewski, ACS Symposium Series 768, 2000).
  • Suitable starting materials include those with a terminal unsaturated carbon-carbon bond, such as anionically-polymerizable monomers (see Hsieh et al., Anionic Polymerization: Principles and Practical Applications , Ch. 5, and 23 (Marcel Dekker, New York, 1996)) and free radically-polymerizable monomers (Odian, Principles of Polymerization, 3 rd Ed., Ch. 3 (Wiley-Interscience, New York, 1991)).
  • Suitable monomers include those that have multiple reaction sites. For example some monomers may have at least two anionically or free radically polymerizable sites. This type of monomer will produce branched polymers. This type of monomer preferably comprises less than 10 molar percent of a given reaction mixture because larger amounts tend to lead to a high degree of crosslinking in addition to branching.
  • Another suitable monomer is one that has at least one functionality that is not anionically-polymerizable in addition to at least one anionically polymerizable site.
  • the temperature-control aspect of the present invention makes it useful for making temperature-sensitive polymers.
  • temperature sensitive polymers include poly(styrenes), poly(dienes), poly((meth)acrylates), and mixtures thereof, as well as polymeric systems that degrade at elevated temperatures over long periods of time.
  • FIG. 1 A system for making polymeric material per the present invention is exemplified by FIG. 1 .
  • initially monomer(s) and solvent(s) are impelled from one or more of feed supplies 12 a - 12 e to purification units 14 a - 14 e via pumps 16 a - 16 e and then into reactor 40 .
  • initiator(s) and quenching agent(s) may be fed directly from feed supplies 12 f and 12 g , respectively, to reactor 40 , for example, by pumps 16 f and 16 g , without passing through a purification unit 14 .
  • initiators can be air-sensitive, it may be desirable to feed the initiator directly to the reactor to avoid excess processing that could introduce air into the initiator supply.
  • Quenching agents typically do not need to be purified because the presence of contaminants should not affect their functioning properly.
  • the number of pumps and the configuration of the system e.g., whether a purification unit is needed, will depend on the number and types of monomers being used.
  • Some components that may be in the reaction mixture such as alkyl lithium reagents, which may be used as initiators, are notoriously sensitive to a variety of deactivating species including, inter alia, H 2 O and O 2 . Therefore, when sensitive reagents are used, care must be taken to remove or exclude such deactivating species from the monomer(s), solvents, and any additives. This removal is performed by purification units 14 a - 14 e.
  • Preferred purification methods include sparging the monomer(s) with an inert gas (e.g., N 2 ) and passing the combined stream of the monomer(s) and any solvent to be used in the initiator solutions through one or more purification columns. Such columns are packed with particles that selectively remove dissolved deactivating species. For example, molecular sieves and a variety of desiccants can remove H 2 O while activated copper can remove O 2 from fluids coming into contact therewith. Those skilled in the art are aware of the importance of removal of H 2 O and O 2 from reaction mixture components as well as numerous ways of accomplishing the same. Low water and oxygen concentrations, i.e., below 10 ppm, ensure that very little initiator or “living” polymer chain is deactivated.
  • an inert gas e.g., N 2
  • Polymerization inhibitors may be removed from monomers by treatment with basic alumina (Al 2 O 3 ) chromatographic materials, as is known in the art. Initiator(s), monomer(s), and solvent(s) are then mixed at the inlet of reactor 40 or are introduced through separate inlets and mixed at some point downstream from the inlet end of reactor 40 .
  • basic alumina Al 2 O 3
  • reaction mixture components typically monomer(s), solvent(s), and initiator(s)
  • component feed supply units e.g., 12 b , 12 c , and 12 d for the monomer/solvent mixture and 12 f for the initiator by pumps 16 b , 16 c , 16 d , and 16 f , respectively.
  • Other monomers, branching agents, functional quenching agent (A fn ), quenching agent (A n ) and solvents can be added to the reactor 40 at some point further downstream from where the initial charge of monomers.
  • additional solvents and monomers may be added from component feed supply units 12 a and 12 e via pumps 16 a and 16 e , respectively.
  • the feed supplies will pass through a corresponding purification unit 14 , if present in the system.
  • a pressure feed i.e., a pressurized tank with a control valve
  • the components preferably are impelled by pump mechanisms.
  • pump mechanisms A wide variety of pump designs can be useful in the present invention as long as the pump seal is sufficient to exclude oxygen, water, and other initiator deactivating materials from feed supply units 12 a - 12 g .
  • Examples of potentially useful pumps include gear pumps, diaphragm pumps, centrifugal pumps, piston pumps, and peristaltic pumps.
  • Some initiator systems are delivered to reactor 40 in the form of a slurry, i.e., a suspension of small particles in a solvent.
  • a slurry i.e., a suspension of small particles in a solvent.
  • butyl lithium can be mixed in cyclohexane for use with diene and vinyl aromatic monomers.
  • Such slurry initiator systems can settle in feed supply unit 12 f and in pump 16 f unless care is taken.
  • a mechanism to keep the initiator system well mixed in feed supply unit 12 f is preferred. Examples of such mechanisms include multiple agitator blades and a pump-around loop.
  • such initiator systems can be impelled to reactor 40 by a pump 16 f that can easily handle slurries. Examples of suitable pumps include peristaltic and diaphragm pumps.
  • Tubing used to transport the reaction mixture components to reactor 40 from 12 a - 12 g must be capable of handling high pressure and of substantially excluding materials capable of deactivating the initiator being used, e.g., water and oxygen.
  • Useful tubing materials include stainless steel, polypropylene, polyethylene, and polytetrafluoroethylene.
  • the tubing preferably is a fluoroelastomer.
  • the rate at which pumps 16 a - 16 g impel the reaction mixture components to reactor 40 can be adjusted so the residence time of the reaction mixture in reactor 40 is at or near a desired length.
  • Typical residence times for STRs having capacities of 0.94, 2, 3.33, 4, 10 and 20 Liters (L) range from as low as five minutes up to about 300 minutes, more typically from about 10 minutes to about 50 minutes, even more typically from about 20 to about 40 minutes, and most typically about 30 minutes.
  • Shorter residence times can result in less waste during changeover (i.e., a change in the type(s) of monomer(s), solvent(s) or initiator(s) being used, the ratio of monomers, the amount(s) of initiator(s), the targeted average molecular weight, etc.) and a substantially reduced response time to process condition changes.
  • feed rates and reaction mixture component concentrations can vary with reactor type and degree of polymerization desired.
  • Reactor 40 can be any type of reactor or reactor design that allows for essentially plug flow of a reaction mixture having a solids loading of above 50 weight %, as well as allowing temperature control of the reaction mixture.
  • the reactor preferably has multiple downstream feed stream injection points. STRs are preferred. The ability to add reagents at numerous points along the reaction pathway in a STR makes the STR well suited for specifically functionalizing the end group structure of a polymer.
  • the reactor has four or more independently temperature controlled zones. A reactor with a single temperature-controlled zone may be used but, if fewer than about four zones are used, the molecular weight polydispersity of the resulting organic material tend to be wider than desired. Notwithstanding the foregoing, when a homopolymer is being made, the reactor preferably has at least two independently temperature controlled zones.
  • reactor 40 Prior to being used in the process of the present invention, reactor 40 may be sweetened. Commonly sweetening is accomplished by filling reactor 40 with a dilute solution of initiator and allowing it to stand for, e.g., about 24 hours. Thereafter, a gaseous sparge and suitable anhydrous solvent can be used to remove the sweetening mixture.
  • Reaction mixture components can be delivered from purification unit 14 and the initiator feed storage unit 12 g to reactor 40 by means of pressure created by pumps 16 a - 16 g . Before reaching reactor 40 , the reaction mixture components optionally can pass through heat exchanger 30 .
  • Optional heat exchanger 30 is used when reactor 40 is to be run at a temperature above or below the temperature of the reaction mixture components prior to being introduced into reactor 40 .
  • the reaction mixture preferably enters the first section of reactor 40 at or near 50° C.
  • optional heat exchanger 30 can be a preheater that raises the temperature of the combined reaction mixture components to approximately that of the first section of reactor 40 .
  • the monomer is initially at room temperature prior to entering the reactor.
  • Reactor 40 can be surrounded by a jacket containing a circulating heat transfer fluid (e.g., water, steam, liquid nitrogen, etc.), which serves as the means to remove heat from or add heat to reactor 40 and the contents thereof.
  • a circulating heat transfer fluid e.g., water, steam, liquid nitrogen, etc.
  • the heat transfer fluid should remain at a relatively low viscosity at the reaction temperature.
  • perfluoroethers are particularly effective at very low temperatures.
  • temperature sensing devices e.g., thermometers and/or thermocouples
  • the temperature and circulation rate of the heat transfer fluid contained in the jacket can be adjusted manually or automatically (e.g., by means of a computer controlled mechanism).
  • reactor 40 can be enclosed by a shroud. Between the exterior of reactor 40 and the shroud is maintained an environment that effectively prevents ignition of any flammable or combustible materials that might be present in or near reaction system 10 .
  • a shroud and the environment permitted thereby) allows general purpose electrical devices (e.g., standard heaters and motors) to be used in or with reaction system 10 .
  • general purpose electrical devices e.g., standard heaters and motors
  • Shrouded reactors are more fully described in U.S. Pat. Nos. 5,814,278, and 5,882,604, which description is incorporated herein by reference.
  • each section of reactor 40 can be maintained at the same (or nearly the same) set temperature, thus ensuring that the reaction mixture encounters a steady temperature profile. This can be done by having separate jackets around each section or having some other means to independently control the temperature of each section. Cyclic temperature profiles also are possible. Alternatively, each successive section of reactor 40 can be maintained at a temperature higher (or lower) that the previous section, thus ensuring that the reaction mixture encounters a rising (or falling) temperature profile.
  • the temperatures at which the zones are maintained will depend on the materials being used and the reaction desired.
  • the objective of controlling the temperature of each section is to ensure that the temperature of the reaction mixture is at a temperature that is conducive to the desired reaction and will not promote unwanted side reactions. If a reactor were long enough it is possible that the reaction mixture temperature could be adequately controlled with a single jacketed zone; however, such a system would be not be particularly efficient.
  • the temperature profile can be altered by changing the temperature of one or more sections. Changing the temperature profile is one way to affect the molecular weight distribution of an organic material for which the polymerization behavior of the monomers can be altered by temperature.
  • Such monomers include methacrylate and vinyl pyridine systems.
  • side reactions that can result in polymers with varying molecular weights can be limited by controlling the temperature of the reaction mixture.
  • the temperature of the reaction mixture will increase whenever monomer is added and polymerization takes place. Therefore, an exothermic reaction may occur when a first monomer is initially fed into the reactor. Another exothermic reaction may occur downstream when a second monomer is added after the first monomer is partially or fully converted and the mixture may have cooled from the initial reaction.
  • an essential feature of reactor 40 is the capability to impel, from the input end of reactor 40 to its output end, in an essentially plug flow manner, the reaction mixture contained therein.
  • essentially plug flow is meant that eddies and dead spots, where reaction mixture can be delayed in its path through reactor 40 , and short circuits to the reactor outlet, which allow the reaction mixture to pass too quickly through reactor 40 , are virtually nonexistent. This means that a given segment of a reaction mixture continues down the length of reactor 40 with about the same velocity profile as a segment traveling therethrough either earlier or later.
  • the manner in which a reaction mixture is impelled through reactor 40 can be by an external means such as a pressure feed (e.g., a pump) or by an internal means (e.g., a screw in an extruder). Plug flow can be assisted by lateral mixing means (e.g., radial paddles in an STR).
  • the reaction mixture preferably has a monomer concentration of 50 to 95 weight percent, and more preferably has a concentration of 60 to 80 weight %. These concentrations allow the reaction mixture to be more easily impelled downstream as polymer forms and increases the viscosity of the reaction mixture.
  • a preferred embodiment of reactor 40 is a stirred tubular reactor (STR), which may consist of a series of cylinders joined together to form a tube. Down the center of this tube, the STR may have a shaft having a plurality of paddles radiating therefrom extends along the primary axis of the tube. (Each cylinder can be jacketed as described previously.) As an external drive causes the shaft to rotate, the paddies stir the reaction mixture and assist in heat transfer. In addition, the paddles can be designed such that they assist the pumps and/or pressure head feed systems in propelling the reaction mixture through the tube.
  • STRs stirred tubular reactor
  • the tube can have a volume ranging from a fraction of a liter to several hundred liters or more depending on the number and radii of the cylinders used.
  • the cylinders can be made of glass, tempered glass, various stainless steels, glass-lined steel, or any other material that is nonreactive with a reaction mixture passing therethrough, can exclude potential initiator deactivating materials (e.g., atmospheric O 2 and H 2 O) from the interior reaction zone, can transfer heat, and can withstand elevated pressure.
  • Preferred materials include 316 L stainless steel and low coefficient of expansion-type glass (e.g., PYREX glass, available from Corning Glass Works; Corning, N.Y.).
  • the cylinders can be joined by means of various types of gaskets and flanges.
  • the tube can be horizontal or angled, it preferably is angled upward from its input end to its output end so as to ensure that any inert gas in the STR can escape through the outlet.
  • the shaft can be made from a variety of inert metals, preferably stainless steel. Where a corrosive initiator such as alkyl lithium is to be used in the STR, the shaft preferably is made from a corrosion resistant stainless steel (e.g., 316 L stainless steel).
  • a corrosion resistant stainless steel e.g., 316 L stainless steel
  • the shaft can be cooled (if desired). This can be accomplished by running a heat transfer fluid, such as water, through it.
  • a heat transfer fluid such as water
  • the paddles can be designed so as to minimize reaction mixture build-up on the paddles and shaft. Build-up often occurs in stagnant regions, which are normally located on the walls of the tube or on the downstream surfaces of paddles, and can result in reduced heat transfer and plugging of the STR. This is of particular importance in polymerizations involving 2- and 4-vinyl pyridine, because the block polymerization of these materials with styrenic or diene monomers produces organized or micellar materials which can be difficult to stir or can settle on reactor walls. Because STRs are cleaned less frequently than batch reactors (and because long term continuous operation is desirable), build-up can result in a loss of residence time. Having to rid an STR of build-up can result in a loss of production time and the introduction of solvents into the STR can deactivate catalyst during future runs. Build-up and the problems resulting therefrom can be minimized by proper paddle design.
  • paddle design can involve the use of cylindrical and/or streamlined designs as well as providing for narrower wall clearances toward the outer end of the STR. (See the Examples section for a description of a preferred type of paddle configuration.)
  • Use of paddles with flexible tips can assist in scraping the walls of the tube.
  • build-up can be minimized by periodically alternating the direction of paddle rotation. Direction can be alternated every few seconds or minutes (or whatever time frame seems to best inhibit build-up with a particular reaction mixture).
  • the STR tube preferably is made from a very strong material (e.g., stainless steel) that can withstand the elevated pressure necessary to assure solubility of the gaseous monomer.
  • a very strong material e.g., stainless steel
  • reactor 40 is a combination system where the output of an STR is pumped into the front end of an extruder.
  • a combination system can take a partially converted reaction mixture exiting an STR and allow for further conversion in an extruder, upon addition of a further aliquot of monomer or by addition of a new monomer. Because the reaction mixture being fed into the extruder is already fairly viscous (e.g., usually 20,000 to several million centipoise), the need for a pressurized feed is eliminated.
  • the STR output is fed to the extruder through a heated line, preferably one that is very short (e.g., up to about three feet).
  • STRs and combinations of STRs and extruders have been mentioned as examples of useful designs for reactor 40 . They are meant to be merely illustrative. Other designs with insubstantial differences (e.g., those that allow for essentially plug flow and temperature control of a mixture with a monomer concentration of above 50 weight %) are within the scope of the present invention when used as reactor 40 .
  • a quench solution may be added to the reaction mixture soon after it exits reactor 40 . This can be accomplished by blending the reaction mixture and quench feeds (not shown) through a simple T-pipe arrangement. To ensure thorough mixing of the two feeds, the combined feed can be fed into another mixer (e.g., a static mixer).
  • another mixer e.g., a static mixer
  • thermal stabilizer e.g., hindered phenols and phosphites
  • thermal stabilizers including hindered phenols and phosphites, are widely used in the industry. Whichever stabilizer is used, it is preferably soluble in the monomer and polymer; otherwise, a solvent will be necessary as a delivery mechanism.
  • unreacted monomer can be stripped out of the reaction mixture by optional devolatization mechanism 50 .
  • devolatization processes include, but are not limited to, vacuum tray drying on, for example, silicone-lined sheets; wiped film and thin film evaporators (when the average molecular weight of the polymer is not too high); steam stripping; extrusion through a spinneret; and air drying.
  • a preferred type of devolatilization mechanism 50 is a DISCOTHERM B high viscosity processor (List AG; Acton, Mass.).
  • DISCOTHERM B high viscosity processor List AG; Acton, Mass.
  • Other manufacturers such as Krauss-Maffei Corp. (Florence, Ky.) and Hosokawa-Bepex (Minneapolis, Minn.) make similar processors. These types of processors have been found to be efficient in separating polymer product from the remainder of the quenched reaction mixture. If desired, such processors can be maintained at below ambient pressures so that reduced temperatures can be used. Use of reduced pressures permit the recapture of very volatile components without extensive degradation of the polymer.
  • reaction mixture i.e., solvent(s), and any quench solution that was used
  • solvent(s) can be disposed of or recycled.
  • the latter option requires that, once condensed, they be separated from each other. This commonly is done by means of distillation; thus, the use of solvent(s) with boiling points that differ significantly from those of the quenching agent solution is preferred.
  • Recycled solvent passes through purification unit 14 prior to being reintroduced into reactor 40 .
  • the average molecular weight and polydispersity of a sample was determined by Gel Permeation Chromatography (GPC) analysis. Approximately 25 mg of a sample was dissolved in 10 milliliters (mL) of tetrahydrofuran (THF) to form a mixture. The mixture was filtered using a 0.2 micron polytetrafluoroethylene (PTFE) syringe filter. Then about 150 microliters ( ⁇ L) of the filtered solution was injected into a Plgel-Mixed B column (available from Polymer Labs, Amherst, Massachusetts) that was part of a GPC system also having a Waters 717 Autosampler and a Waters 590 Pump.
  • GPC Gel Permeation Chromatography
  • the system operated at room temperature, with a THF eluent that moved at a flow rate of approximately 0.95 mL/min.
  • An Erma ERC-7525A Refractive Index Detector was used to detect changes in concentration.
  • Number average molecular weight (M n ) and polydispersity index (PDI) calculations were based on a calibration mode that used narrow polydispersity polystyrene controls ranging in molecular weight from 6 ⁇ 10 2 to 6 ⁇ 10 6 . The actual calculations were made with Caliber software available from PolymerLabs.
  • sample The average molecular weight and polydispersity of some samples were determined via a triple detection method as described. Samples were prepared by the addition of 10 ml of tetrahydrofuran to approximately 25 mg of sample. The solutions were filtered using a 0.2 micron PTFE syringe filter. 100 microliters of each sample solution was injected into a column set consisting of 3 ⁇ Plgel Mixed-B 10 micron GPC columns, maintained at 40° C. (Eppendorf Column Heater).
  • MALLS Wyatt Technology MiniDAWN EOS Multi-Angle Laser Light Scattering
  • each block was determined by Nuclear Magnetic Resonance (NMR) spectroscopy analysis. A sample was dissolved in deuterated chloroform to a concentration of about 10 wt % and placed in a Unity 500 MHz NMR Spectrometer available from Varian, Palo Alto, Calif. Block concentrations were calculated from relative areas of characteristic block component spectra.
  • NMR Nuclear Magnetic Resonance
  • the STR had a capacity of 3.33 L and consisted of five jacketed (shell-and-tube) glass sections (Pyrex cylinders).
  • the tube had an inner diameter of 4.13 cm and an outer diameter of 5.08 in.
  • the shell had a diameter of 8.89 cm.
  • the sections were 60.96 cm long, two are 30.48 cm long, and one is 68.58 cm long. These were arranged in an alternating short-long fashion with the longest being last.
  • the sections were joined together with stainless steel connector disks.
  • the STR was closed off at both ends with stainless steel disks.
  • the connector disks were equipped with individual temperature sensing devices extending into the interior of the cylindrical sections. These temperature-sensing devices permitted the temperature of the reaction mixture in each section to be monitored and adjusted up or down (as necessary) to a set point by varying the temperature of the heat transfer fluid flowing through the jacketed sections.
  • Extending through the center of the joined cylinders was a 0.95 cm diameter stainless steel shaft suspended along the cylinder axis by shaft alignment pins.
  • To the shaft were affixed 60 detachable stainless steel paddles with approximately 2.1 cm between each paddle.
  • the rectangular paddles were 3.2 mm thick, 1.91 cm wide, and 3.81 cm long.
  • the paddle configurations used was as follows; in section 1 , 14 rectangular paddles; in section 2 , seven rectangular paddles; in section 3 , 14 rectangular paddles; in section 4 , seven rectangular paddles; and in section 5 , 18 rectangular paddles.
  • the shaft was attached to a 2.2 kW variable speed motor and driven at approximately 150 rpm.
  • the STR had a capacity of 4 L and consisted of one 316 stainless steel inlet section (21.59 cm long by 5.48 cm in diameter) and four additional stainless steel sections (316 SS), each with an outside diameter of 6.03 cm, an inside diameter of 5.48 cm, and alternating lengths of 67.31 cm and 38.58 cm. These were joined together with stainless steel clamps.
  • the STR was closed off at both ends with stainless steel disks, and the cylindrical sections were enclosed with jackets made of stainless steel.
  • the jackets were equipped with individual temperature sensing devices extending into the interior of the cylindrical sections. These temperature sensing devices permitted the temperature of the reaction mixture in each section to be monitored and adjusted up or down (as necessary) to a set point by varying the temperature of the heat transfer fluid flowing through the jacketed sections.
  • the reactant monomers in the examples were nitrogen sparged until the O 2 concentration was less than 1 part per million (ppm).
  • the purified monomer was then fed directly to the first zone of a stirred tubular reactor (STR) when used for the initial block, or at a later zone of the STR for a subsequent block formation.
  • Reaction solvents either toluene, cyclohexane or a mixture
  • the THF also was deoxygenated by nitrogen sparging for 30 minutes and purified by pumping through both 3A molecular sieve beads (available as Zeolite 3A, UOP) and a column of alumina (available as Al 2 O 3 , Aldrich, Brockmann I, 150 mesh,).
  • the THF stream was then fed directly to the first or second zone of the STR.
  • a sec-butyl lithium initiator 1.3 Molar (M) sec-butyl lithium in cyclohexane
  • pre-purified cyclohexane for example 2 and 3, 1,1 diphenylhexyl lithium was used.
  • the initiators were added to the first zone of the STR
  • This example exemplifies that diene and styrene block copolymer materials, an important class of controlled architecture materials, can be made by this invention at high solids loading levels.
  • An initiator slurry was prepared by mixing 2300 g of 1.3 M sec-butyl lithium in cyclohexane with 8000 g of oxygen-free cyclohexane and stirred at room temperature for about 30 minutes. The stirring was done under nitrogen to prevent stratification and oxygen contamination. Purified styrene monomer (delivered at various rates via reciprocating piston pump, see Table 1) and purified cyclohexane solvent (delivered at a rate of 19-20 g/min via reciprocating piston pump) were passed into zone 1 of the 3.3 Liter STR. The initiator slurry was introduced by peristaltic pump at a rate of 24 ml/min into zone 1 of the STR. The solids loading of this reaction was varied as shown in Table 1.
  • zone 1 A color change, from clear to red-orange, was observed in zone 1 when the initiator solution contacted the monomer, and an exotherm resulted.
  • the inlet temperature of zone 1 was 53.8° C.
  • the mixture in zone 1 was kept constant at about 27° C. by adjusting the jacket temperature of zone 1 to 20° C.
  • the materials flowed through the first zone of the STR facilitated by the stirring paddles along the reaction path. Polymerization continued to 100% completion by the end of zone 1 , thereby forming a “living” polystyrene reaction mixture polymer.
  • purified isoprene was delivered at various rates (via reciprocating piston pump, see Table 1) and purified THF (pressure fed at a rate of 3 g/min), resulting in a strong exotherm with a color change from red to yellow indicating the formation of polystyrene-isoprene block copolymers.
  • the combined residence time for these reactions in the STR varied between 19 and 28 minutes, depending upon constituent flow rates (see Table 1).
  • This example illustrates the ability to make methacrylic homopolymers and block copolymers under very high solids conditions.
  • An initiator slurry was prepared by mixing 775.9 ml of 1.3 M sec-butyl lithium in cyclohexane with 4133 g of oxygen-free cyclohexane and stirred at room temperature for about 30 minutes. To this solution was added 196 g of 1,1-diphenylethylene, which resulted in the formation of a red colored solution of 1,1-diphenylhexyl lithium. Purified 2-ethylhexyl methacrylate monomer (pumped via a reciprocating piston pump at a rate of 89.3 g/min) was fed into zone 1 of the 3.3 Liter STR.
  • the initiator solution was introduced by peristaltic pump at a rate of 35 ml/min into zone 1 of the STR along with a 1.0 M solution of triisobutyl aluminum (pressure fed at 19.8 g/min). When the initiator solution contacted the monomer an exotherm resulted (about 23° C.).
  • t-BMA was added via reciprocating piston pump at a flow rate of 8 g/min into zone 5 of the STR and allowed to proceede through the reactor.
  • Samples of PEHMA and P(EHMA-t-BMA) were taken at various times. Each sample was tested for number average molecular weight (Mn) and Polydispersity Index (PDI) by Gel Permeation Chromatography. The identity of the polymer and examination of the reaction mixture for residual monomer was conducted by 1 H NMR spectroscopy. Results are shown in Table 2.
  • This example illustrates the making of homo, block, random and star polymers at very high solids levels.
  • An initiator slurry was prepared by mixing 780 ml of 1.3 M sec-butyl lithium in cyclohexane with 8000 g of oxygen-free cyclohexane and stirred at room temperature for about 30 minutes. To this solution was added 197 g of 1,1-diphenylethylene, which resulted in the formation of a red colored solution of 1,1-diphenylhexyl lithium.
  • a 1 wt % solution of 1,6-hexanediol dimethacrylate (HDDMA) was made by pre-dissolving 40 g of HDDMA in 4000 g of purified cyclohexane.
  • the initiator solution was introduced by peristaltic pump at a rate of 24 ml/min into zone 1 of the 3.3 Liter STR along with a 1.0 M solution of triisobutyl aluminum (pressure fed at 4.5 g/min).
  • Purified 2-ethylhexyl methacrylate (EHMA), t-butyl methacrylate (t-BMA) and HDDMA streams were delivered via a reciprocating piston pump at various rates and to various locations of the STR, depending upon the targeted architecture (see Table 3).
  • This example illustrates that a free radical polymerization mechanism can be employed in this invention to produce random, functional group-containing polymers in this approach.
  • the polymerization was taken to greater than 95% conversion through control of temperatures and concentration of chain transfer reagent.
  • the monomer solids loading for this reaction was 65 wt %.
  • An initiator solution was prepared by mixing 500 g of t-butyl peroxybenzoate with 10,700 g of O 2 -free o-xylene and stirred at room temperature for about 30 minutes. Mixing 15808 g of IOA, 3952 g of IBA and 1040 g of HEMA under a nitrogen atmosphere and sparging the mixture for 30 minutes prepared a solution of IOA:IBA:HEMA.
  • the IOA:IBA:HEMA mixture (pumped via a reciprocating piston pump at a rate of 43.3 g/min) was preheated to 68 C by passage through an external heat exchanger and the t-butyl peroxybenzoate/o-xylene stream (pumped a reciprocating piston pump at a rate of 23.3 g/min) were fed into zone 1 of a 4 Liter STR.
  • the first zone on the STR was heated to 130° C. by means of low-pressure steam, resulting in an exotherm.
  • the materials flowed through the first four zones in a plug-like fashion, facilitated by stirring paddles along the reaction path.
  • Zones 2 and 3 were heated with 5 psi of steam (about 100-105° C.) to help facilitate movement of the polymer through the reactor.
  • This polymerization continued to very high conversion forming an IOA:IBA:HEMA copolymer.
  • the total non-optimized residence time for these reactions was approximately 60 minutes.
  • This example illustrates that a free radical polymerization mechanism can be employed in this invention to produce random, functional group-containing polymers in this approach.
  • the polymerization is taken to greater than 95% conversion through control of temperatures and concentration of chain transfer reagent.
  • the monomer solids loading for this reaction is 80 wt %.
  • An initiator solution was prepared by mixing 361 g of t-butyl peroxybenzoate with 3400 g of O 2 -free o-xylene and stirred at room temperature for about 30 minutes. Mixing 11433 g of IOA, 2858 g of IBA and 752 g of HEMA under a nitrogen atmosphere and sparging the mixture for 30 minutes prepared a solution of IOA:IBA:HEMA.
  • the IOA:IBA:HEMA mixture (pumped via a reciprocating piston pump at a rate of 80.1 g/min) was preheated to 64° C.
  • zone 1 of the 4 Liter STR was heated to 130° C. by means of low-pressure steam, resulting in an exotherm.
  • the materials flowed through the first four zones in a plug-like fashion, facilitated by stirring paddles along the reaction path.
  • Zones 2 and 3 were heated with 5 psi of steam (about 100-105° C.) to help facilitate movement of the polymer through the reactor.
  • the total un-optimized residence time for these reactions was about 40 minutes.
  • This example illustrates that a free radical polymerization mechanism can be employed in this invention to produce random, functional group-containing polymers in this approach.
  • the polymerization is taken to greater than 95% conversion through control of temperatures and concentration of chain transfer reagent.
  • the monomer solids loading for this reaction is 95 wt %.
  • An initiator solution was prepared by mixing 500 g of t-butyl peroxybenzoate with 596 g of O 2 -free o-xylene and stirred at room temperature for about 30 minutes. Mixing 15833 g of IOA, 3958 g of IBA and 1041 g of HEMA under a nitrogen atmosphere and sparging the mixture for 30 minutes prepared a solution of IOA:IBA:HEMA. The IOA:IBA:HEMA mixture (pumped via an FMI at a rate of 95 g/min) was preheated to 68° C.
  • zone 1 of the 4 Liter STR was heated to 130° C. by means of low-pressure steam, resulting in an exotherm.
  • the reaction temperature was not controlled by external measures.
  • the materials flowed through the first four zones in a plug-like fashion, facilitated by stirring paddles along the reaction path.
  • Zones 2 and 3 were heated with 5 psi of steam (about 100-105° C.) to help facilitate movement of the polymer through the reactor.

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EP1572750A1 (en) 2005-09-14
JP2006511657A (ja) 2006-04-06
MXPA05006329A (es) 2005-08-26
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BR0317115B1 (pt) 2014-01-28
EP1572750B1 (en) 2013-06-19

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